KR102023165B1 - Photo-curable and thermo-curable resin composition and dry film solder resist - Google Patents

Abstract

The present invention provides a photocurable functional group having an acrylate group or an unsaturated double bond, and an acid-modified oligomer having a carboxyl group in a molecule thereof; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; Plate-shaped inorganic fillers having an E-modulus of 90 to 120 (Gpa); It relates to a resin composition having a photocurable and thermosetting and a dry film solder resist prepared therefrom, including a dispersant and a photoinitiator.

Description

Resin composition and dry film soldering resist which have photocurability and thermosetting TECHNICAL FIELD [TECHNICAL Citation] AND DRY FILM SOLDER RESIST}

The present invention relates to photocurable and thermosetting resin compositions and dry film solder resists. More specifically, the present invention is capable of forming a fine pattern required in a dry film solder resist (DFSR), and having a photocurable and thermosetting resin composition having excellent mechanical properties, low thermal expansion coefficient, and high modulus. It relates to a dry film solder resist having one characteristic.

BACKGROUND ART With the miniaturization and light weight of various electronic devices, photosensitive solder resists capable of forming fine opening patterns are used for printed circuit boards, semiconductor package substrates, and flexible circuit boards.

Semiconductor packaged products are composite materials consisting of epoxy molding, insulators such as solder resists, semiconductors such as chip dies, and conductors such as substrate circuit patterns, which require a number of processes involving severe thermal shock conditions. However, due to the difference in the coefficient of thermal expansion (CTE) of each of the insulators, semiconductors, and conductors, dimensional instability and warpage of the component appear as problems. This phenomenon causes a mismatch between the chip and the substrate when soldering the chip die and the semiconductor substrate with solder balls or gold wires, and also causes the product to crack and break due to shear stress, which may affect the life of the product. Can be.

Recently, as the thickness of the substrate becomes thinner, such dimensional instability and warpage are becoming more problematic. In order to solve this problem, materials are being developed to minimize CTE mismatch between materials, and solder resists are continuously required to be developed as solder resists having a lower coefficient of thermal expansion.

The previously known dry film solder resist (DFSR) has a coefficient of thermal expansion of 45 to 70 ppm of α1 (coefficient of thermal expansion before Tg) and 140 to 170 ppm of α2 (coefficient of thermal expansion after Tg).

Recently, materials having a thermal expansion coefficient of 10 ppm or less or 5 ppm or less have been developed in the case of the core of the substrate material, but the development of a solder resist material that can be used with it has not been known until now.

In addition, there have been attempts to lower the thermal expansion coefficient of the solder resist by increasing the content of the filler, but if the content of the filler is raised above a certain level, coating failure may occur due to the aggregation of the filler. Problems such as decrease in workability may appear.

The solder resist generally requires characteristics such as developability, high resolution, insulation, adhesion, soldering heat resistance, gold plating resistance, and the like. In particular, for solder resists for semiconductor package substrates, in addition to these characteristics, for example, the crack resistance for the temperature cycle test (TCT) of -65 ° C to 150 ° C or the HAST (Highly Accelerated Stress Test between fine wirings). ) Characteristics are required.

In recent years, as a soldering resist, the dry-film type soldering resist which has favorable film thickness uniformity, surface smoothness, and thin film formability attracts attention. Such a dry film type solder resist may have advantages such as simplification of the process for forming the resist and reduction of solvent emissions during the resist formation in addition to the above characteristics.

Conventionally, in order to form a soldering resist, the resin composition which has photocurability and thermosetting, including photopolymerizable monomers, such as a polyfunctional acrylate, with an acid-modified oligomer, a photoinitiator, and a thermosetting binder, was used. However, the solder resist formed from such a resin composition does not have a high glass transition temperature and is not sufficient in heat resistance reliability, so that the PCT resistance, TCT heat resistance, and HAST resistance between the fine wirings required for the package substrate material of the semiconductor device are adequate. There was a disadvantage that could not be met.

In addition, the Young's modulus value of the conventional solder resist is 3 to 5 Gpa, which depends on the filler content of 5 to 20 vol% of the solder resist solids. In addition, the Young's modulus when using only resin in a soldering resist without adding a filler is 2.5 Gpa level.

In order to increase the modulus and lower the CTE, it is common practice to increase the filler content, but when the filler content exceeds 20 vol% of the solder resist solids, it is disadvantageous to form a fine pattern.

The present invention provides a dry film-type solder resist that satisfies the basic physical properties required for dry film-type solder resists, in particular, has a low coefficient of thermal expansion and excellent mechanical properties, high modulus, fine patterns, and favorable bending. It is providing the resin composition which has photocurability and thermosetting.

In addition, the present invention, while meeting the basic physical properties required in the dry film-type solder resist, in particular has a low coefficient of thermal expansion and excellent mechanical properties, high modulus, fine pattern is possible and advantageous to the dry film type solder resist ( DFSR).

The present invention provides a photocurable and thermosetting resin composition having excellent mechanical properties of a film type useful for producing a package substrate of a semiconductor device, and a dry film resist using the cured product thereof.

In the present specification, an acid-modified oligomer having a photocurable functional group having an acrylate group or an unsaturated double bond and a carboxyl group in a molecule thereof; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; Plate-shaped inorganic fillers having an E-modulus of 90 to 120 (Gpa); It includes; dispersant and photoinitiator,

The plate-shaped inorganic filler has a whiteness of 90% or more, a particle size (D50) of 0.5 to 2 μm, a top size of 3 to 10 μm, and a moisture of 0.3 to 1% as measured by JIS-K5101. Photocurable and thermoset comprising a plate-like talc powder having a content and an apparent density of 0.07 to 0.2 (g / ml) and a specific surface area of 17 to 30 (m2 / g) measured by the BET method. It provides a resin composition.

Preferably, the plate-shaped inorganic filler, whiteness of 96% or more, particle size (D50) of 0.6 to 1.5㎛, Top size of 4 to 7㎛, 0.5 to 0.7 measured by JIS-K5101 And a plate-like talc powder having a water content of% and an apparent density of 0.09 to 0.1 (g / ml) and a specific surface area of 18 to 24 (m2 / g) measured by the BET method.

The plate-shaped inorganic filler may be included in 20% by weight to 60% by weight in solids of the total composition. Further, preferably, the plate-shaped inorganic filler may be included in 40% by weight to 55% by weight in solids of the total composition.

The acid-modified oligomer may include an epoxy (meth) acrylate-based compound.

The acid-modified oligomer may be included in 5% by weight to 75% by weight based on the total weight of the resin composition.

The photopolymerizable monomer may include an acrylate compound having two or more photocurable unsaturated functional groups.

The photopolymerizable monomer may be a hydroxyl group-containing acrylate compound, a water-soluble acrylate compound, a polyester acrylate compound, a polyurethane acrylate compound, an epoxy acrylate compound, a caprolactone modified acrylate compound, or two kinds thereof. It may contain a mixture of the above.

The photopolymerizable monomer may be included in 5 to 30% by weight based on the total weight of the resin composition.

The photoinitiator is a group consisting of benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides and oxime esters. It may include one or more selected from.

The photoinitiator may be included in 0.5 to 20% by weight based on the total weight of the resin composition.

The thermosetting functional group may be at least one selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.

The thermosetting binder may be included in an amount corresponding to 0.5 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.

The resin composition which has the said photocurability and thermosetting property is a solvent; And an epoxy curing agent, a thermosetting binder catalyst, pigments, and additives.

In the present specification, an acid-modified oligomer having a photocurable functional group having an acrylate group or an unsaturated double bond and a carboxyl group in a molecule thereof; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product between thermosetting binders having a thermosetting functional group, and a plate-shaped inorganic filler having an E-modulus of 90 to 120 (Gpa) dispersed in the cured product.

The cured product may include a crosslinked structure in which a photocurable functional group of the acid-modified oligomer and a thermosetting functional group of the thermosetting binder are crosslinked; A crosslinked structure in which a photocurable functional group of the acid-modified oligomer and an unsaturated functional group of the photopolymerizable monomer are crosslinked with each other; And it may include a crosslinked structure derived from the acid-modified oligomer.

The dry film solder resist may have a coefficient of thermal expansion of less than 20 ppm / K.

The dry film solder resist may have a Young's modulus of 9 to 11 Gpa.

The plate-shaped inorganic filler has a whiteness of 90% or more, a particle size (D50) of 0.5 to 2 μm, a top size of 3 to 10 μm, and a moisture content of 0.3 to 1% as measured by JIS-K5101. And plate-shaped talc powder having an apparent density of 0.07 to 0.2 (g / ml) and a specific surface area of 17 to 30 (m2 / g) measured by the BET method.

The dry film solder resist may include the plate-shaped inorganic filler as 20 wt% to 60 wt% of the solder resist solids.

According to the present invention, by using a photosensitive resin composition containing a plate-shaped inorganic filler having a high modulus and specific physical properties together with a dispersant, it has a particularly low thermal expansion coefficient and excellent mechanical properties while satisfying the basic physical properties required in a dry film solder resist. A dry film type solder resist (DFSR) may be provided, which may have high modulus, have a fine pattern, and may be advantageous in bending.

1 is an electron micrograph (SEM) showing the results of forming a micropattern of Example 1 and Comparative Examples 1 to 5 of the present invention.
FIG. 2 is a graph illustrating comparison of Young's modulus according to filler contents of Examples 1 to 3 and Comparative Examples 1 to 5 of the present invention.
Figure 3 is a graph showing the thermal expansion coefficient according to the temperature of Examples 1 to 3 and Comparative Examples 1, 2 and 4.

Hereinafter, a photocurable and thermosetting resin composition and an DFSR according to an embodiment of the present invention will be described in more detail.

According to one embodiment of the invention, a photocurable functional group having an acrylate group or an unsaturated double bond, an acid-modified oligomer having a carboxyl group in the molecule; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; Plate-shaped inorganic fillers having an E-modulus of 90 to 120 (Gpa); Dispersing agent and photoinitiator, wherein the plate-shaped inorganic filler, whiteness of 90% or more, particle size (D50) of 0.5 to 2㎛, Top size of 3 to 10㎛, by JIS-K5101 It comprises a plate-like talc powder having a water content of 0.3 to 1%, an apparent density of 0.07 to 0.2 (g / ml) and a specific surface area of 17 to 30 (m2 / g) measured by the BET method. The resin composition which has photocurability and thermosetting property is provided.

The resin composition which has photocurable and thermosetting of this invention means the photosensitive resin composition. Such a resin composition of the present invention, by using a plate-shaped inorganic filler having a specific modulus and containing a certain amount, even if the filler content exceeds 20 vol% of the solder resist solid content, the micropattern required in the solder resist is possible and low thermal expansion Coefficient (CTE) and high modulus can be achieved. Therefore, the present invention can provide a dry film type solder resist which is advantageous in warpage and excellent in mechanical properties.

The E-modulus refers to "young's modulus", which is an elastic modulus indicating the degree of stretching and deformation of an object when the object is stretched from both sides, and specifically, a universal test machine according to ISO 527 and ASTM D638 standards. Can be measured by the device.

The photocurable and thermosetting resin composition includes the acid-modified oligomer, photopolymerizable monomer, photoinitiator, thermosetting binder, and plate-shaped inorganic filler and dispersant having specific properties.

The DFSR may be formed by the following process using the resin composition of the above embodiment. First, after forming a film with a resin composition and laminating such a film on a predetermined board | substrate, it selectively exposes to the resin composition of the part in which DFSR is to be formed. Subsequently, when development is carried out using an alkali developer, the resin composition of the exposed part having the crosslinked structure is left on the substrate as it is, and the resin composition of the remaining non-exposed part may be dissolved in the developer and removed.

Then, when the resin composition remaining on the substrate is thermally cured by heat treatment, the acid-modified oligomer, for example, a carboxyl group, may react with a thermosetting functional group of the thermosetting binder to form a crosslink. As the crosslinked structure is formed by thermosetting, DFSR may be formed in a desired portion on the substrate.

In this case, the resin composition may have a secondary crosslinked structure in the thermosetting process. Also In the case of forming the DFSR using the resin composition, the crosslinked structure is included in the cured product of the resin composition constituting the DFSR and the amount of other remaining compounds is minimized, thereby ensuring higher developability and thus fine pitch. (fine pitch) can be implemented more easily. In addition, by using the resin composition having photocurability and thermosetting property, it is possible to provide a dry film solder resist having physical properties such as low alpha particle emission degree, low dielectric constant, low thermal expansion coefficient, and excellent heat resistance. In particular, the composition may provide DFSR with minimal warpage and excellent mechanical properties.

The photocurable and thermosetting resin composition may include 20 wt% to 60 wt% (solid content) of the plate-shaped inorganic filler in solid content of the entire composition. And when this solid content is converted into the volume ratio in a resin composition, it may correspond to 20-40 vol% or 30-35 vol% of solid content of the whole resin composition.

The plate-shaped inorganic filler has a whiteness of 90% or more, a particle size (D50) of 0.5 to 2 μm, a top size of 3 to 10 μm, and a moisture content of 0.3 to 1% as measured by JIS-K5101. And plate-shaped talc powder having an apparent density of 0.07 to 0.2 (g / ml) and a specific surface area of 17 to 30 (m2 / g) measured by the BET method.

Specifically, the plate-shaped inorganic filler has a whiteness of 96% or more, a particle size (D50) of 0.6 to 1.5 μm, a top size of 4 to 7 μm, and 0.5 to 0.7% measured by JIS-K5101. It may be desirable to include plate-like talc powder having a water content of 0.09 to 0.1 (g / ml) and an apparent density of 18 to 24 (m2 / g) measured by the BET method. .

The photocurable and thermosetting resin composition of the embodiment may include 20 wt% to 60 wt%, or 40 to 55 wt%, or 45 wt% to 55 wt% of the inorganic filler in the solid content of the total composition. . If the content of the inorganic filler is too small, the hardness and stiffness of the final DFSR is not sufficiently secured workability may be low, the effect of the addition of the above-described inorganic filler may not be sufficiently expressed. In addition, if the content of the inorganic filler is too high, the inorganic filler is not easily dispersed in the resin composition having the photocurable and thermosetting of the embodiment, the viscosity of the resin composition is greatly increased and is not easy to apply on the substrate As a result, it may be difficult to manufacture the dry film solder resist, and the elongation of the dry film solder resist may be lowered.

In this case, the solid content of the plate-shaped inorganic filler in the entire resin composition in the present invention means that it is calculated in consideration of only the components except for the solvent and volatile matter.

In addition, the volume ratio content of the said plate-shaped inorganic filler in the whole resin composition means what was calculated in consideration of the density of a filler and resin, respectively.

Hereinafter, the resin composition according to one embodiment will be described in more detail for each component.

Acidity  Oligomer

In the resin composition, the resin used with the filler has a higher crystallinity tendency, and a higher inter / infra interation is advantageous. In other words, the higher the attraction between the polymer chains, the better.

Such a resin composition of one embodiment typically comprises a well-known acid-modified oligomer.

Acid-modified oligomers include carboxyl groups and photocurable functional groups such as photocurable functional groups having acrylate groups or unsaturated double bonds, and oligomers having carboxyl groups in a molecule, and have been known to be used in resin compositions for forming DFSR. All ingredients can be used without restriction. For example, the main chain of such additional acid-modified oligomer may be a novolak epoxy or polyurethane, or the like. A component having a carboxyl group and an acrylate group introduced therein may be used as an additional acid-modified oligomer. The photocurable functional group may preferably be an acrylate group, wherein the acid-modified oligomer may be obtained as an oligomer form by copolymerizing a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound.

More specifically, specific examples of additional second acid-modified oligomers usable in the resin composition include the following components:

(1) Obtained by copolymerizing unsaturated carboxylic acids (a) such as (meth) acrylic acid and compounds (b) having unsaturated double bonds such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene Carboxyl group-containing resins;

(2) ethylenically unsaturated groups such as vinyl groups, allyl groups, (meth) acryloyl groups, epoxy groups, acid chlorides, and the like, as part of the copolymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by making a compound which has a reactive group, for example, glycidyl (meth) acrylate react, and adding an ethylenically unsaturated group as a pendant;

(3) to a copolymer of a compound (c) having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate and a compound (b) having an unsaturated double bond; Carboxyl group-containing photosensitive resin obtained by making unsaturated carboxylic acid (a) react, and making saturated or unsaturated polybasic acid anhydride (d), such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride, react with the produced | generated secondary hydroxy group;

(4) One hydroxy group such as hydroxyalkyl (meth) acrylate in a copolymer of an acid anhydride (e) having an unsaturated double bond such as maleic anhydride and itaconic anhydride and a compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by making compound (f) which has 1 or more ethylenically unsaturated double bond react;

(5) The epoxy group of the polyfunctional epoxy compound (g) which has two or more epoxy groups in the molecule mentioned later, or the polyfunctional epoxy resin in which the hydroxy group of the polyfunctional epoxy compound was further epoxidized with epichlorohydrin, (meth The carboxyl group of unsaturated monocarboxylic acid (h) such as acrylic acid is subjected to esterification reaction (full esterification or partial esterification, preferably total esterification) and further saturated or unsaturated polybasic acid anhydride (d) Carboxyl group-containing photosensitive compound obtained by making it react;

(6) 1 in 1 molecule of an alkyl group having 2 to 17 carbon atoms, an aromatic group-containing alkyl carboxylic acid, etc., in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate A carboxyl group-containing resin obtained by reacting an organic acid (i) having two carboxyl groups and not having an ethylenically unsaturated bond and reacting a saturated or unsaturated polybasic acid anhydride (d) with the resulting secondary hydroxy group;

(7) diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; and carboxyl group-containing dialcohol compounds (k) such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarboxes; Diol compounds such as carbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adducts, diols, phenolic hydroxyl groups and compounds having alcoholic hydroxyl groups ( carboxyl group-containing urethane resin obtained by the polyaddition reaction of m);

(8) diisocyanate (j), bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, non Photosensitive properties obtained by polyaddition reaction of (meth) acrylate or partial acid anhydride modified product (n) of bifunctional epoxy resins, such as a phenol type epoxy resin, its carboxyl group-containing dialcohol compound (k), and a diol compound (m) Carboxyl group-containing urethane resin;

(9) Compound (f) having one hydroxy group such as hydroxyalkyl (meth) acrylate and one or more ethylenically unsaturated double bonds is added during the synthesis of the resin of the above (7) or (8) and unsaturated at the terminal. Carboxyl group-containing urethane resin which introduce | transduced the double bond;

(10) A compound having one isocyanate group and one or more (meth) acryloyl groups in a molecule such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin (7) or (8). Carboxyl group-containing urethane resin which was added and terminal (meth) acrylated;

(11) Saturated or unsaturated polybasic anhydrides with respect to the primary hydroxy group in the modified oxetane compound obtained by reacting unsaturated monocarboxylic acid (h) with a polyfunctional oxetane compound having two or more oxetane rings in a molecule as described later. carboxyl group-containing photosensitive resin obtained by making (d) react;

(12) Carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then making a saturated or unsaturated polybasic acid anhydride (d) react;

(13) Novolak-type phenol resins, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon Unsaturated monocarboxylic acid (h) is reacted with a reaction product with cyclic carbonates such as carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, and saturated or unsaturated polybasic acid. Carboxyl group-containing photosensitive resin obtained by making anhydride (d) react;

Among the above-mentioned components, in the said (7)-(10), when the isocyanate group containing compound used for resin synthesis becomes diisocyanate which does not contain a benzene ring, and in said (5) and (8), When the polyfunctional and bifunctional epoxy resins used in the synthesis are linear compounds having bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton or bixylenol skeleton, or hydrogenated compounds thereof, the flexibility and the like of DFSR The component which can be preferably used as an acid-modified oligomer can be obtained. In addition, in another aspect, the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.

In addition, commercially available components may be used as the acid-modified oligomer described above, and specific examples of such components include ZAR-2000, CCR-1235, ZFR-1122 or CCR-1291H, etc.

More specific examples of the acid-modified oligomers include epoxy (meth) acrylate compounds. The epoxy (meth) acrylate compound means a reactant between an epoxy compound or a polyepoxy compound and 2) a (meth) acrylate compound or a hydroxy (meth) acrylate compound.

By using the epoxy (meth) acrylate-based compound, DFSR can sufficiently secure the flexibility and the like of DFSR, exhibit a lower coefficient of thermal expansion and improved heat resistance, and can be preferably used as a package substrate material of a semiconductor device. This may be provided.

As said epoxy (meth) acrylate type compound, the epoxy (meth) acrylate compound derived from cresol novolak or the epoxy (meth) acrylate compound derived from bisphenol F can be used. In addition, the epoxy (meth) acrylate compound is an epoxy (meth) acrylate compound derived from cresol novolak and an epoxy (meth) acrylate compound derived from bisphenol F 4: 1 to 1: 1 by weight, or 3 It may be included in a weight ratio of 1: 1 to 2: 1.

The epoxy (meth) acrylate-based compound may have a weight average molecular weight of 5,000 to 50,000, or 6,000 to 20,000. If the weight average molecular weight of the epoxy (meth) acrylate-based compound is too large, the ratio of photocurable acrylate may be relatively reduced, which may lower developability or lower the strength of DFSR. If the weight average molecular weight of the epoxy (meth) acrylate compound is too small, precipitation or aggregation of filler particles may occur during inorganic filler dispersion, and the resin composition of one embodiment may be excessively developed.

The acid-modified oligomer may be included in 5% by weight to 75% by weight, or 10% by weight to 50% by weight based on the total weight of the resin composition. Further, optionally, the photocurable and thermosetting resin composition may comprise 5% to 75% by weight of the acid-modified oligomer and the second acid-modified oligomer including the carboxyl group and the photocurable unsaturated functional group based on the total weight, or 10 wt% to 50 wt% may be included.

When the content of the acid-modified oligomer is too small, the developability of the resin composition may be lowered and the strength of the DFSR may be lowered. On the contrary, when the content of the acid-modified oligomer is too high, not only the resin composition may be excessively developed, but also uniformity may be decreased during coating.

In addition, the acid value of the acid-modified oligomer may be about 40 to 200 mgKOH / g, or about 50 to 150 mgKOH / g, or about 60 to 120 mgKOH / g. When the acid value is too low, alkali developability may be lowered. On the contrary, when the acid value is too high, it may be possible to dissolve the photocurable portion, for example, the exposed portion, by the developing solution, which makes it difficult to form a normal pattern of the DFSR.

Photopolymerizable  Monomer

Meanwhile, the resin composition of one embodiment includes a photopolymerizable monomer. Such a photopolymerizable monomer may be, for example, a compound having a photocurable unsaturated functional group such as two or more polyfunctional vinyl groups, and may form a crosslink with the unsaturated functional group of the acid-modified oligomer described above to provide photocuring during exposure. Crosslinked structure can be formed. Thereby, the resin composition of the exposure part corresponding to the part where DFSR is to be formed can be left on the substrate without alkali development.

As the photopolymerizable monomer, a liquid phase may be used at room temperature, and accordingly, the viscosity of the resin composition of one embodiment may be adjusted according to the coating method, or the role of improving the alkali developability of the non-exposed part may also be combined.

As the photopolymerizable monomer, an acrylate compound having two or more photocurable unsaturated functional groups can be used, and more specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Hydroxyl group-containing acrylate compounds such as triacrylate or dipentaerythritol pentaacrylate; Water-soluble acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethylolpropane or hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; Polyfunctional or monofunctional polyurethane acrylate compounds which are isocyanate modified products of the hydroxyl group-containing acrylate; Epoxy acrylate compounds that are (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or phenol novolac epoxy resins; Caprolactone-modified acrylate compounds such as caprolactone-modified ditrimethylolpropane tetraacrylate, acrylate of ε-caprolactone-modified dipentaerythritol, or caprolactone-modified hydroxypivalatene neopentyl glycol ester diacrylate, And one or more compounds selected from the group consisting of photosensitive (meth) acrylate compounds such as methacrylate compounds corresponding to the acrylate compounds described above, and these may be used alone or in combination of two or more thereof. .

Among these, as said photopolymerizable monomer, the polyfunctional (meth) acrylate type compound which has two or more (meth) acryloyl groups in 1 molecule can be used preferably, Especially pentaerythritol triacrylate and a trimethylol propane Triacrylate, dipentaerythritol hexaacrylate, caprolactone modified ditrimethylol propane tetraacrylate, etc. can be used suitably. As an example of a commercially available photopolymerizable monomer, Kaylarad DPEA-12 etc. are mentioned.

The photopolymerizable monomer may be included in 1 to 30% by weight, or 2 to 20% by weight based on the total weight of the resin composition. If the content of the photopolymerizable monomer is too small, the photocuring may not be sufficient, and if the content of the photopolymerizable monomer is too large, the drying property of the DFSR may deteriorate and the physical properties may be degraded.

Photoinitiator

The resin composition of one embodiment includes a photoinitiator. Such a photoinitiator, for example, serves to initiate radical photocuring between the acid-modified oligomer and the photopolymerizable monomer in the exposed portion of the resin composition.

As a photoinitiator, a well-known thing can be used and benzoin, such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Materials such as these can be used.

In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -One, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone ( As commercially available products, α-aminoacetophenones such as Irugacure (registered trademark) 907, Irugacure 369, Irugacure 379, etc. of Chiba Specialty Chemical Co., Ltd. (currently Chiba Japan Co., Ltd.), 2,4,6- Trimethylbenzoyldiphenylhospinoxite, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide ( As a commercial item, acyl phosphine oxides, such as Rucillin (trademark) TPO by BASF Corporation and Irgacure 819 by Chivas Specialty Chemical Co., Ltd.), etc. can be mentioned as a preferable photoinitiator.

Moreover, oxime ester is mentioned as a preferable photoinitiator. Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthene-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, and 2- (O-benzoyloxime ), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), and the like. Commercially available products include GGI-325 from Chiba Specialty Chemical, Irugacure OXE01, Irugacure OXE02, ADEKA N-1919, Chiba Specialty Chemical's Darocur TPO, and the like.

The content of the photoinitiator may be about 0.5 to 20% by weight, or about 1 to 10% by weight, or about 1 to 5% by weight based on the total weight of the resin composition. If the content of the photoinitiator is too small, photocuring may not occur properly, on the contrary, if the content of the photoinitiator is too large, the resolution of the resin composition may be lowered or the reliability of the DFSR may not be sufficient.

Thermosetting binder

The resin composition of one embodiment also includes a thermosetting binder having at least one member selected from thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups. Such a thermosetting binder may form a crosslinking bond with an acid-modified oligomer and the like by thermosetting to secure heat resistance or mechanical properties of DFSR. In addition, the type of the thermosetting binder is not limited, and materials well known in the art may be used.

As the thermosetting binder, a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule can be used, and a bifunctional epoxy resin can be used. have. Other diisocyanates or their difunctional block isocyanates can also be used.

The thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having any one or two or more of three, four or five membered cyclic ether groups, or cyclic thioether groups in the molecule. have. The thermosetting binder may be a polyfunctional epoxy compound having at least two epoxy groups in a molecule, a polyfunctional oxetane compound having at least two oxetanyl groups in a molecule, or an episulfide resin having two or more thioether groups in a molecule And so on.

As a specific example of the said polyfunctional epoxy compound, bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, for example , Phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyc Oxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone modified epoxy resin and (epsilon) -caprolactone modified epoxy resins. In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. By thermosetting these epoxy resins, characteristics, such as adhesiveness of a cured film, solder heat resistance, and electroless plating resistance, are improved.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers and copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, charixarenes, carlixresolecinarenes, or silses And etherates with resins having hydroxy groups such as quoxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has two or more cyclic thioether group in the said molecule | numerator, bisphenol A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used.

Moreover, as marketed, YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.

The thermosetting binder may be included in an amount corresponding to about 0.5 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer. For example, the photocurable and thermosetting resin composition may include 0.1 to 30% by weight, or 0.1 to 10% by weight of the thermosetting binder. When the content of the thermosetting binder is too small, the carboxyl group remains in the DFSR after curing, the heat resistance, alkali resistance, electrical insulation may be lowered. On the contrary, when the content is too large, it is not preferable because the low molecular weight cyclic (thio) ether group remains in the dry coating film because the strength and the like of the coating film decrease.

Plate  weapon filler

What is considered at high elastic modulus in dry film type solder resist is young's modulus represented by the following equation.

[Equation 1]

=

=

=

=

=

=

In Equation 1, E is the Young's modulus, F is the force exerted on the material under tension, A ₀ is the original cross section to which the force is applied, ΔL is the change in the length of the material, and L ₀ is the original length of the material.

In order to provide a high elastic modulus, it is preferable that the modulus Eα of the filler itself is high in the resin composition and the soldering resist, and the filling shape is high, and the filler shape is advantageous in the direction in which the surface area is maximized. Specifically, the aspect ratio in the shape of the filler increases in the shape of a sphere, a cube, and a plate, and it is preferable that the resin-filler uses a plate-shaped filler to maximize the contact area.

Based on such a point, this invention is characterized by using the plate-shaped inorganic filler which has a high modulus and has a specific physical property.

Preferably, the E-modulus of the plate-shaped inorganic filler may be 90 to 120 (Gpa). In addition, it is preferable that the plate-shaped inorganic filler uses talc powder having a specific physical property having the high E-modulus described above.

More preferably, the plate-shaped inorganic filler, the whiteness of 90% or more, the particle size (D50) of 0.5 to 2㎛, the top size of 3 to 10㎛, 0.3 to 0.3 measured by JIS-K5101 Platelet talc powder having a moisture content of 1% and an apparent density of 0.07 to 0.2 (g / ml) and a specific surface area of 17 to 30 (m2 / g) measured by the BET method.

Most preferably, the plate-shaped inorganic filler has a whiteness of 96% or more, a particle size (D50) of 0.6 to 1.5 μm, a top size of 4 to 7 μm, and 0.5 to 0.5 measured by JIS-K5101. Platelet talc powder having a water content of 0.7% and an apparent density of 0.09 to 0.1 (g / ml) and a specific surface area of 18 to 24 (m2 / g) measured by the BET method.

In this case, when the inorganic filler does not satisfy the above physical properties, for example, when the inorganic filler particle size is less than 0.6 um, the specific surface area is relatively increased, and the contact area between the resin and the filler becomes too large, so that the adhesion between the dry coating film and the PCB substrate is increased. There is a problem of this deterioration. On the other hand, when the inorganic filler particle size exceeds 2 um, it adversely affects fine pattern formation.

The plate-shaped inorganic filler serves to improve heat stability, thermal dimensional stability, and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color.

In addition, in the present invention, conventional inorganic or organic fillers may be further used as necessary, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, clay, magnesium carbonate, calcium carbonate, Aluminum oxide (alumina), aluminum hydroxide, mica and the like can be used.

In addition, in the present invention, the plate-shaped inorganic filler is preferably used to correspond to 20 to 40 vol%, more preferably 30 to 35 vol% of the solid content of the entire resin composition. The volume% of the filler in the solid content of the total resin composition may be used in the following content ranges.

That is, the plate-shaped inorganic filler may be 20% to 60% by weight, or 40 to 55% by weight, or 45% to 55% by weight in solids of the total composition. When the solid content of the inorganic filler is used in excess of 60% by weight, the viscosity of the composition is increased, so that the coating property is lowered or the degree of curing is lowered, which is not preferable. In addition, when the solid content is less than 20% by weight, the modulus improvement effect may not be expected, and developability and thermal expansion coefficient may decrease.

At this time, the solid content of the plate-shaped inorganic filler in the entire resin composition in the present invention can be calculated in consideration of only the components except the solvent and volatile matter.

In addition, the volume ratio content of the plate-shaped inorganic filler in the total resin composition may be calculated in consideration of the density of each of the filler and the resin.

Dispersant

In addition, in the present invention, the use of the plate-shaped inorganic filler can form a fine pattern even when the inorganic filler is used in an excess of 35% by weight or more with respect to the solid content, but in the case of using only the plate-shaped inorganic filler, the filling amount must be increased so that the fine pattern can be formed. May be disadvantageous.

Therefore, in this invention, it has the characteristic to use a predetermined amount including a dispersing agent in a resin composition with the plate-shaped inorganic filler mentioned above. That is, the dispersant is used to improve the dispersion stability of the filler, pigment, etc., it is easy to form a fine pattern.

The dispersant may be used in an appropriate amount in consideration of the dispersibility of each component used in the photosensitive resin composition, for example, the dispersant is included in 1 to 6% by weight based on the total solids weight of the resin composition. desirable. If the amount of the dispersant is too small, less than 1% by weight, the dispersion may not be sufficient and may be detrimental to the formation of the micropattern, and when the amount of the dispersant is added in excess of 6% by weight, the heat resistance and reliability may be affected. Can be crazy Therefore, if only the inorganic filler is used without the dispersing agent, no micropattern is formed even if it exhibits a certain modulus value.

Dispersants used in the present invention include Dorf Ketal's Tyzor AA, AA-65, AA-105 and the like.

On the other hand, in addition to each component described above, the resin composition of one embodiment is a solvent; And at least one selected from the group consisting of an epoxy curing agent, a thermosetting binder catalyst, a pigment, and an additive to be described later.

Thermosetting binder catalyst

The thermosetting binder catalyst serves to promote thermosetting of the thermosetting binder.

As such a thermosetting binder catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound) by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N and UCAT3502T by San Apro Corporation (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. It is not specifically limited to these, It may be the thing which accelerates reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, It can also be used individually or in mixture of 2 or more types. . Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isosaururic acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting binder catalyst.

The used content of the thermosetting binder catalyst may be about 0.3 to 2% by weight based on the total solid weight of the resin composition in terms of suitable thermosetting.

Pigment

Pigments exhibit visibility and hiding power to hide defects such as scratches on circuit lines.

As the pigment, red, blue, green, yellow, black pigments and the like can be used. As the blue pigment, phthalocyanine blue, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 60, and the like can be used. have. Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. may be used as the green pigment. Examples of the yellow pigments include anthraquinones, isoindolinones, condensed azos, and benzimidazolones. For example, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment. Pigment yellow 181, pigment yellow 193 and the like can be used.

The content of the pigment is preferably used at about 0.5 to 3% by weight based on the total weight of the resin composition. When used in less than 0.5% by weight, visibility and hiding power is lowered, and when used in excess of 3% by weight is less heat resistance.

additive

The additive may be added to remove bubbles in the resin composition or remove popping or craters from the surface of the film, impart flame retardancy, adjust viscosity, and catalyze the film.

Specifically, known conventional thickeners such as finely divided silica, organic bentonite and montmorillonite; Antifoaming agents and / or leveling agents such as silicone, fluorine, and polymers; Silane coupling agents such as imidazole series, thiazole series, and triazole series; Known and common additives such as flame retardants such as phosphorus flame retardants and antimony flame retardants can be blended.

Among them, the leveling agent serves to remove the popping or craters of the surface when the film is coated, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350, etc. of BYK-Chemie GmbH.

The content of the additive is preferably about 0.01 to 10% by weight based on the total weight of the resin composition.

solvent

One or more solvents may be used in combination to dissolve the resin composition or impart an appropriate viscosity.

As a solvent, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Acetate esters, such as these; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbitol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylacetamide and dimethylformamide (DMF). These solvents can be used alone or as a mixture of two or more thereof.

The content of the solvent may be about 1 to 50% by weight based on the total weight of the resin composition. If it is less than 1% by weight, the viscosity is high, the coating property is inferior, and if it exceeds 50% by weight, the drying is not good and the stickiness is increased.

On the other hand, according to another embodiment of the present invention, a photocurable functional group having an acrylate group or an unsaturated double bond, an acid-modified oligomer having a carboxyl group in a molecule; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product between thermosetting binders having thermosetting functional groups, and a plate-shaped inorganic filler having an E-modulus of 90 to 120 (Gpa) dispersed in the binder.

Referring to the process of manufacturing a dry film solder resist (DFSR) using the photocurable and thermosetting resin composition of the embodiment is as follows.

First, the resin composition of the embodiment as a photosensitive coating material on a carrier film is used as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater or After coating with a spray coater or the like, the oven at 50 ° C to 130 ° C is dried for 1 to 30 minutes and dried, and then a release film is laminated to form a carrier film, a photosensitive film, and a release from below. The dry film comprised from a film can be manufactured.

The photosensitive film may have a thickness of about 5 to 100 μm. In this case, a plastic film such as polyethylene terephthalate (PET), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film may be used as the carrier film, and polyethylene (PE), A polytetrafluoroethylene film, a polypropylene film, a surface treated paper, or the like can be used, and when the release film is peeled off, it is preferable that the adhesive force of the photosensitive film and the release film is lower than that of the photosensitive film and the carrier film.

Next, after peeling off a release film, the photosensitive film layer is bonded together on the board | substrate with a circuit using a vacuum laminator, a hot roll laminator, a vacuum press, etc.

Next, the substrate is exposed to light (UV, etc.) having a constant wavelength band. The exposure may be selectively exposed with a photo mask or may be directly pattern exposed with a laser direct exposure machine. The carrier film peels off after exposure. Although exposure amount changes with coating film thickness, 0-1,000 mJ / cm <2> is preferable. When the exposure is performed, for example, in the exposed portion, photocuring may occur to form a crosslink between the acid-modified oligomer and the unsaturated functional groups included in the photopolymerizable monomer and the like, and as a result, the crosslinking may not be eliminated by subsequent development. Can be in a state. On the contrary, the non-exposed part may not be formed with the crosslinked structure and thus the crosslinked structure, and thus the carboxyl group may be maintained to be in an alkali developable state.

Next, development is carried out using an alkaline solution or the like. The alkaline solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. By this phenomenon, only the film of the exposed portion may remain.

Finally, by heat curing (Post Cure), a printed circuit board including a solder resist formed from the photosensitive film is completed. The heat curing temperature is preferably at least 100 ° C.

Through the above-described method, a DFSR and a printed circuit board including the same may be provided. The DFSR may be acid-modified oligomer including a carboxyl group and a photocurable unsaturated functional group as it undergoes photocuring and thermosetting; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured liver of a thermosetting binder having a thermosetting functional group. In addition, the dry film solder resist may include a plate-type inorganic filler dispersed in the binder and having the above-described specific physical properties.

More specifically, the cured product may include a crosslinked structure in which a photocurable functional group of the acid-modified oligomer and a thermosetting functional group of the thermosetting binder are crosslinked; A crosslinked structure in which a photocurable functional group of the acid-modified oligomer and an unsaturated functional group of the photopolymerizable monomer are crosslinked with each other; And it may include a crosslinked structure derived from the acid-modified oligomer.

In addition, as the photocurable and thermosetting resin composition for preparing the dry film solder resist of the embodiment further includes a second acid-modified oligomer including a carboxyl group and a photocurable unsaturated functional group, the cured product included in the DFSR is a carboxyl group. And acid-modified oligomers including photocurable unsaturated functional groups; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product between thermosetting binders having thermosetting functional groups.

The dry film solder resist of the above embodiment contains a crosslinked product including a triazine crosslinked structure, but minimizes the amount of other remaining compounds, thereby ensuring higher developability and thus making fine pitch easier. Can be implemented.

In addition, the present invention includes a plate-shaped inorganic filler having a high modulus and exhibiting specific physical properties, thereby lowering the coefficient of thermal expansion and improving Young's modulus. In particular, by including a certain amount of the dispersant together with the inorganic filler, it is possible to form a fine pattern and to implement a high modulus.

Accordingly, the dry film solder resist may have a coefficient of thermal expansion of less than 40 ppm / K, and preferably may have a coefficient of thermal expansion of 15 to 30 ppm / K.

In addition, the dry film solder resist may have a Young's modulus of 4 to 12 GPa. Preferably, the dry film solder resist may have a Young's modulus of 7 to 10 GPa.

In addition, the DFSR may have a high glass transition temperature of about 120 ° C. to 180 ° C., for example, or about 140 to 170 ° C., and may exhibit improved heat resistance reliability. Accordingly, the DFSR satisfies various physical properties such as excellent PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for the package substrate material of the semiconductor device, and can be preferably used as the package substrate material of the semiconductor device.

In addition, the DFSR may further include a small amount of photoinitiator remaining in the cured product after participating in photocuring.

As mentioned above, according to the present invention Since the dry film solder resist includes a plate-shaped inorganic filler dispersed in the cured product, the dry film solder resist is effective in improving modulus and lowering of CTE, and also has a high level with respect to a substrate that is commonly used while sufficiently securing the hardness of the manufactured DFSR. Adhesion can be maintained.

In addition, the DFSR may include a form in which a conventional inorganic filler is further dispersed as necessary.

The plate-shaped inorganic filler has a whiteness of 90% or more, a particle size (D50) of 0.5 to 2 μm, a top size of 3 to 10 μm, and a moisture of 0.3 to 1% as measured by JIS-K5101. Plate-like talc powder having a content and an apparent density of 0.07 to 0.2 (g / ml) and a specific surface area of 17 to 30 (m2 / g) measured by the BET method.

More preferably, the plate-shaped inorganic filler, whiteness of 96% or more, particle size (D50) of 0.6 to 1.5㎛, Top size of 4 to 7㎛, 0.5 to 0.5 measured by JIS-K5101 Platelet talc powder having a water content of 0.7% and an apparent density of 0.09 to 0.1 (g / ml) and a specific surface area of 18 to 24 (m2 / g) measured by the BET method.

The dry film soldering resist of the embodiment may include 20 wt% to 60 wt%, more preferably 40 wt% to 55 wt%, or 45 wt% to 55 wt% of the plate-shaped inorganic filler having the physical properties. If the solid content of the inorganic filler in the solder resist is too small, the hardness and stiffness of the DFSR may not be sufficiently secured, the workability may be low, the effect of the addition of the above-described inorganic filler may not be sufficiently expressed. have. In addition, if the solid content of the inorganic filler is too high, the inorganic filler is not uniformly dispersed in the DFSR, the elongation of the dry film solder resist may be reduced.

Details of components that may be included in the dry film solder resist include the above-described contents with respect to the photocurable and thermosetting resin composition of the embodiment.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

[ Example  And Comparative example : Manufacture of Resin Composition, Dry Film and Printed Circuit Board]

Example 1

45 g of CCR-1171H as acid-modified oligomer, 15 g of ZAR-2000, 5 g of DPHA as a photopolymerizable monomer, 4 g of TPO as a photoinitiator, 18 g of YDCN-500-80P as a thermosetting binder, 2-PI 1 g as a thermosetting binder catalyst 68 g of Talc (NANO ACE D-800) (Nippon Talc CO., LTD.) With a particle size (D50) of 0.8 μm as a plate-shaped inorganic filler, 0.5 g of phthalocyanine blue (B15: 3) as a pigment and 0.5 g of Y147 as a dispersant. 4 g of Tyzor AA and 50 g of solvent DMF were mixed to prepare a resin composition. At this time, the E-modulus of the plate-shaped talc NANO ACE D-800 was 115 Gpa.

The resin composition prepared above was applied to PET as a carrier film, dried through 100 ovens, and then laminated with PE as a release film to form a carrier film, a photosensitive film (thickness 20 μm), and a release film from below. A dry film was prepared.

After removing the cover film of the manufactured dry film, the photosensitive film layer was vacuum-laminated on the board | substrate with a circuit, the photomask corresponding to the circuit pattern was put on the photosensitive film layer, and it exposed by UV. Exposure progressed UV of the 365 nm wavelength band by the exposure amount of 400 mJ / cm <^2> . Thereafter, the PET film was removed, and developed with a Na ₂ CO ₃ 1% by weight alkaline solution at 31 ° C. for a predetermined time to remove unnecessary portions to form a desired pattern. Subsequently, photocuring was performed at an exposure dose of 1500 mJ / cm ² , and finally heat curing was performed at 160 to 170 ° C. for 1 hour to complete a printed circuit board including a protective film (solder resist) formed from the photosensitive film. .

Example 2

Dry film and printing in the same manner as in Example 1, except that the type of inorganic filler was changed to 68 g of NANO ACE D-1000 (Nippon Talc CO., LTD.) Having a particle size (D50) of 1.0 μm. A circuit board was prepared.

At this time, the E-modulus of the plate-shaped talc NANO ACE D-1000 was 120 Gpa.

Example 3

Dry film and printed circuit in the same manner as in Example 1, except that the content of the plate-type inorganic filler was changed to 86 g of NANO ACE D-1000 (Nippon Talc CO., LTD.) Having a particle size (D50) of 1.0 μm. The substrate was prepared.

At this time, the E-modulus of the plate-shaped talc NANO ACE D-1000 was 120 Gpa.

Specific compositions of the resin compositions of Examples 1 to 3 are as summarized in Table 1 below.

Example 1 Example 2 Example 3 ingredient Ingredients Self Solid
(weight%) a b a b a b A CCR-1171H 65 45 29.25 45 29.25 45 29.25 ZAR-2000 65 15 9.75 15 9.75 15 9.75 B DPHA 100 5 5 5 5 5 5 C YDCN-500-80P 100 18 18 18 18 18 18 D TPO 100 4 4 4 4 4 4 E 2-PI 100 One One One One One One F NANO ACE D-800 100 68 68 0 0 NANO ACE D-1000 100 0 68 68 86 86 G Phthalocyanine blue (B15: 3) 100 0.5 0.5 0.5 0.5 0.5 0.5 Y147 100 0.5 0.5 0.5 0.5 0.5 0.5 H Tyzor AA 75 4 3 4 3 4 3 I DMF 0 50 0 50 0 50 0 Sum 211 139 211 139 229 157 Filler weight in solids (g) 68 68 86 Resin ditch in solids (g) 71 71 71 Filler weight in solids (wt%) 48.9 48.9 54.8 Resin weight in solids (wt%) 51.1 51.1 45.2 Filler Volume in Solids (ml) 18.1 18.1 20.3 Resin Volume in Solids (ml) 42.6 42.6 37.7 Filler Volume Ratio in Solids (vol%) 29.9 29.9 35 A: acid-modified oligomer, B: photopolymerizable monomer, C: thermosetting monomer, D: photoinitiator E: catalyst, F: inorganic filler, G: pigment, H: dispersant, I: solvent
a: raw material component (g)
b: solid weight (g)

In Table 1, the solid content of the plate-shaped inorganic filler in the total resin composition was calculated in consideration of only the components except for the solvent and the volatile component. Non-100% solids in raw materials are as follows:

65wt% solid content of CCR-1171H

65wt% solids of ZAR-2000

75 wt% solids of Tyzor AA.

In addition, the volume ratio content of the said plate-shaped inorganic filler in the total resin composition was calculated in consideration of the density of each of the filler and the resin: (volume = mass / density)

Density of Talc (NANO ACE) 2.7

Assuming that the resin was cured at a density of 1.2, each solid content (g) was divided by density to obtain a volume, and a volume ratio (vol%) was obtained therefrom.

Comparative Example 1

A dry film and a printed circuit board were manufactured in the same manner as in Example 2, except that the plate-shaped inorganic filler was not used.

Comparative Example 2

A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that 25 g of spherical silica (SFP-120M, manufactured by Denka) was used without using a plate-shaped inorganic filler.

Comparative Example 3

A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that 76 g of spherical silica (SFP-120M, manufactured by Denka) was used without using a plate-shaped inorganic filler.

At this time, the E-modulus of Denka SFP-120M of the spherical silica was 70 Gpa.

Comparative Example 4

A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that 174 g of spherical silica (SFP-120M, manufactured by Denka) was used without using a plate-shaped inorganic filler.

Comparative Example 5

A dry film and a printed circuit board were used in the same manner as in Example 1, except that a plate-shaped inorganic filler was used, except that plate-shaped talc (Micro Ace P-3, Nippon talc) having an E-modulus of 120 Gpa (D50 5.0 μm) was used. Was prepared.

Specific compositions of the resin compositions of Comparative Examples 1 to 5 are as summarized in Tables 2 and 3 below.

Comparative Example 1 Comparative Example 2 ingredient Ingredients Self Solid
(weight%) a b a b A CCR-1171H 65 45 29.25 45 29.25 ZAR-2000 65 15 9.75 15 9.75 B DPHA 100 5 5 5 5 C YDCN-500-80P 100 18 18 18 18 D TPO 100 4 4 4 4 E 2-PI 100 One One One One F NANO ACE D-800 100 0 0 0 0 NANO ACE D-1000 100 0 0 0 0 Denka SFP-120M 100 0 25 25 G Phthalocyanine blue (B15: 3) 100 0.5 0.5 0.5 0.5 Y147 100 0.5 0.5 0.5 0.5 H Tyzor AA 75 4 3 4 3 I DMF 0 50 0 50 0 Sum 143 71 168 96 Filler weight in solids (g) 0 25 Resin ditch in solids (g) 71 71 Filler weight in solids (wt%) 0 26 Resin weight in solids (wt%) 100 74 Filler Volume in Solids (ml) 0 10.9 Resin Volume in Solids (ml) 83.3 61.6 Filler Volume Ratio in Solids (vol%) 0 15 A: acid-modified oligomer, B: photopolymerizable monomer, C: thermosetting monomer, D: photoinitiator
E: catalyst, F: inorganic filler, G: pigment, H: dispersant, I: solvent
a: raw material component (g)
b: solid weight (g)

Comparative Example 3 Comparative Example 4 Comparative Example 5 ingredient Ingredients Self Solid
(weight%) a b a b a b A CCR-1171H 65 45 29.25 45 29.25 45 29.25 ZAR-2000 65 15 9.75 15 9.75 15 9.75 B DPHA 100 5 5 5 5 5 5 C YDCN-500-80P 100 18 18 18 18 18 18 D TPO 100 4 4 4 4 4 4 E 2-PI 100 One One One One One One F NANO ACE D-800 100 0 0 0 0 0 0 NANO ACE D-1000 100 0 0 0 0 0 0 Micro ace
P-3 100 0 0 0 0 68 68 Denka SFP-120M 100 76 76 174 1740 0 0 G Phthalocyanine blue (B15: 3) 100 0.5 0.5 0.5 0.5 0.5 0.5 Y147 100 0.5 0.5 0.5 0.5 0.5 0.5 H Tyzor AA 75 4 3 4 3 4 3 I DMF 0 50 0 50 0 50 0 Sum 219 147 317 245 211 139 Filler weight in solids (g) 76 174 68 Resin ditch in solids (g) 71 71 71 Filler weight in solids (wt%) 51.7 71 48.9 Resin weight in solids (wt%) 48.3 29 51.1 Filler Volume in Solids (ml) 21.5 29.6 18.1 Resin Volume in Solids (ml) 40.2 24.1 42.6 Filler Volume Ratio in Solids (vol%) 34.9 55.1 29.9 A: acid-modified oligomer, B: photopolymerizable monomer, C: thermosetting monomer, D: photoinitiator
E: catalyst, F: inorganic filler, G: pigment, H: dispersant, I: solvent
a: raw material component (g)
b: solid weight (g)

In Tables 2 and 3, the solid content of the plate-shaped inorganic filler in the total resin composition was calculated in consideration of only the components except for the solvent and the volatile component. Non-100% solids in raw materials are as follows:

65wt% solid content of CCR-1171H

65wt% solids of ZAR-2000

75 wt% solids of Tyzor AA.

In addition, the volume ratio content of the said plate-shaped inorganic filler in the total resin composition was calculated in consideration of the density of each of the filler and the resin: (volume = mass / density)

Density of Talc (NANO ACE) 2.7

Density of Silica (SFP-120M) 2.4.

Assuming that the resin was cured at a density of 1.2, each solid content (g) was divided by density to obtain a volume, and a volume ratio (vol%) was obtained therefrom.

< Experimental Example  >

The physical properties of the dry film and the printed circuit board prepared in Examples and Comparative Examples were measured by the following method:

Experimental Example 1 : Glass transition temperature ( Tg ) Measure

On the Shiny surface of 3EC-M3-VLP 12 micrometer copper foil of Mitsui Metals, the film layer was laminated | stacked similarly to the preparation of the measurement specimens, such as PCT heat resistance. Except that the negative type mask having a stripe pattern having a width of 5 mm and a spacing of 5 mm was placed on the specimen and exposed, the DFSR specimen was subjected to heat curing in the same manner as in the preparation of the measurement specimen such as moisture absorption and heat resistance of Experimental Example 1. Produced. Finally, the copper foil was peeled from the specimen to prepare a 5 mm striped specimen for TMA (thermal mechanical analysis, METTLER TOLEDO, TMA / SDTA 840) evaluation.

Glass transition temperature (Tg) was measured by the following method. First, the specimen was mounted on a holder to have a length of 10 mm, and the length of the specimen was measured under a condition of a temperature increase rate of 5 / min from -20 ° C. to 300 ° C. while applying force at both ends to 0.05 N. The inflection point seen in the temperature increase section was Tg, and Tg was evaluated by the following method:

1: Tg 150 ° C. or higher;

2: Tg 120 degreeC or more and less than 150 degreeC;

3: Tg 100 degreeC or more and less than 120 degreeC;

4: Tg less than 100 ° C.

And the coefficient of thermal expansion (CTE) simultaneously required by the Tg measurement was measured and compared at the same time. First, the coefficient of thermal expansion was calculated from the slope of the specimen increased from 0 ° C to 100 ° C. The results of these calculations were evaluated under the following criteria:

(Coefficient of Thermal Expansion)

1: less than 15 ppm / K;

2: 15 ppm / K or more but less than 20 ppm / K;

3: 20 ppm / K or more and less than 30 ppm / K;

4: 30 ppm / K or more.

Experimental Example 2 : Developability  evaluation

The 3EC-M3-VLP 12 micrometer copper foil laminated board of Mitsui Metals was cut into the horizontal X length = 5 cm X 5 cm size, and fine roughness was formed in the copper foil surface by chemical etching. After removing the release film of the dry film manufactured by the said Example and the comparative example, the said film layer was vacuum laminated on the copper foil laminated board (board | substrate) in which roughness was formed by the vacuum laminator (MV LP-500 by Meisei Seisakusho Co., Ltd.). .

And the negative type photomask which has a hole shape from 100 micrometers in diameter to 10 micrometers in diameter unit was contact | adhered, and UV of 365 nm wavelength band was exposed by the exposure amount of 400mJ / cm <^2> . Thereafter, the PET film was removed, and developed with a Na ₂ CO ₃ 1 wt% alkaline solution at 31 ° C. for a period of time to form a pattern. The shape of the formed pattern was observed by SEM, and evaluated under the following criteria.

1: Developable up to 30 μm hole diameter or less

2: Developable to hole diameters of 40 to 50 μm

3: Developable to hole diameter 50 to 60 µm

4: Developable or undeveloped only hole diameter 60 ㎛ or more

Experimental Example 3 : Permittivity measurement

The 15 cm * 15 cm sized dry film solder resists obtained in Examples and Comparative Examples were laminated onto a 16 cm * 16 cm sized copper foil, except that the entire area was exposed at an exposure dose of 400 mJ / cm ² without a photo mask. In the same manner as in the preparation of measurement specimens such as moisture absorption heat resistance of Experimental Example 1, heat curing was performed and only copper foil was etched to prepare a DFSR specimen (cured film).

For the cured film, dielectric constant in the 10 GHz band was measured using Agilent Technologies Inc.'s Vector Network Analyzer as a measuring instrument and QWED's Split Post Dieletrci Resonator as a measuring jig.

The results measured and evaluated in Experimental Examples 1 to 3 are summarized in Table 4 below.

Example Comparative example One 2 3 One 2 3 4 5 Tg 2 2 2 3 3 4 4 2 CTE
(ppm) 2 2 One 4 4 2 One 2 Developability 2 2 2 2 2 4 4 4 permittivity 3.5 3.5 3.5 3.2 3.5 3.5 3.5 3.4

As shown in the measurement and evaluation results of Table 4, the DFSR of the Example is greatly improved developability, exhibiting superior physical properties in comparison with the DFSR of the comparative example in the physical properties such as heat resistance, glass transition temperature, thermal expansion coefficient, dielectric constant, etc. This was confirmed. Therefore, it was confirmed that the example is suitable for the formation of DFSR showing high temperature heat resistance reliability.

On the other hand, Comparative Examples 1 to 5 can be seen that the physical properties than the overall Examples 1 to 3. In addition, Comparative Example 5 showed some physical properties, but the development characteristics were found to be inferior to the Examples. That is, in the case of Comparative Example 5 even if E-modulus is included in the scope of the present application, D50 is too large as 5um occurred a problem that greatly developability.

Experimental Example 4 : Fine pattern

For Example 1 and Comparative Examples 1 to 5, E-modulus and electron micrographs (SEM) were measured, and the results are shown in FIG. 1.

Referring to FIG. 1, in Comparative Example 1, no filler was applied, and although a pattern was formed to some extent, a micropattern could not be realized and E-modulus was also low. In Comparative Examples 3 and 4, the E-modulus showed a level similar to that of the present application, but in the case of Comparative Examples 2 to 4, spherical fillers were applied, and thus the micropattern could not be realized. In particular, as can be seen from the SEM photograph of Comparative Example 5, the pattern itself was not formed.

On the other hand, Example 1 contained about 68 vol (solid content 48.9 wt%) of the plate-shaped inorganic filler and the dispersant of about 30 vol% of the total solids, it was confirmed that the fine pattern can be formed.

Experimental Example 5 : Young's modulus Modulus

Young's modulus modulus was measured by the conventional method about the 15 cm * 15 cm size dry film soldering resist obtained by the Example and the comparative example. In addition, the Young's modulus modulus according to the filler content is shown in FIG.

As shown in FIG. 2, Comparative Example 1 exhibited a very low Young's modulus because no filler was applied, and Comparative Examples 2 to 4 increased Young's modulus by increasing the filling amount than Comparative Example 1, but spherical filler was used. It has a disadvantageous result in the formation of the micropattern. At this time, Comparative Example 4 has a higher Young's modulus than Examples 1 to 3 of the present application, but as described in FIG. 1, it was impossible to form a fine pattern. And, in Comparative Example 5, although the heat modulus modulus showed a tendency similar to that of the present application, the particle size of the filler was so large that it greatly degraded the developability and thus no pattern was formed.

On the other hand, Examples 1 to 3 showed overall Young's modulus better than Comparative Examples 1 to 5. In particular, Example 3 was able to form a micropattern using 86 g of plate-shaped filler (volume content 54.8% by weight) and a dispersant of 35 vol% of the total solids, in particular the Young's modulus modulus reached a level of 10 Gpa.

Experimental Example 6 : CTE  evaluation

In measuring the thermal expansion coefficient, the section was changed and the results of Examples 1 to 3 and Comparative Examples 2 to 4 were compared. That is, the coefficient of thermal expansion was calculated as the slope of the specimen increased from 0 ℃ to 100 ℃ section. At this time, Cu foil was used as 13um, and this calculation result is shown in FIG. 3.

In Figure 3, it can be seen that compared to Comparative Examples 2 to 4 using the inorganic filler, the coefficient of thermal expansion coefficient of Examples 1 to 3 using the plate-shaped inorganic filler and dispersant in the content range of the present application is low.

Claims (22)

Acid-modified oligomers having a photocurable functional group having an acrylate group or an unsaturated double bond and a carboxyl group in a molecule;
Photopolymerizable monomers having two or more photocurable unsaturated functional groups;
Thermosetting binders having thermosetting functional groups;
Plate-shaped inorganic fillers having an E-modulus of 90 to 120 (Gpa);
Dispersants; And
A photoinitiator;
The plate-shaped inorganic filler has a whiteness of 96% or more, a particle size (D50) of 0.6 to 1.5 μm, a top size of 4 to 7 μm, and a water content of 0.5 to 0.7% measured by JIS-K5101. And plate-shaped talc powder having an apparent density of 0.09 to 0.1 (g / ml) and a specific surface area of 18 to 24 (m2 / g) measured by the BET method,
Said plate-shaped inorganic filler contains 40 to 55 weight% in solid content of the whole composition, The resin composition which has photocurability and thermosetting.
delete delete delete The resin composition of claim 1, wherein the dispersant comprises 1 to 6 wt% based on the total solids weight of the resin composition.
The method of claim 1,
The acid-modified oligomer is a resin composition having a photocurable and thermosetting comprising an epoxy (meth) acrylate-based compound.
The method of claim 1,
The acid-modified oligomer is a resin composition having a photocurable and thermosetting comprising 5% to 75% by weight based on the total weight of the resin composition.
The method of claim 1,
The photopolymerizable monomer comprises a photocurable and thermosetting resin composition comprising an acrylate compound having two or more photocurable unsaturated functional groups.
The method of claim 1,
The photopolymerizable monomer is selected from the group consisting of a hydroxyl group-containing acrylate compound, a water-soluble acrylate compound, a polyester acrylate compound, a polyurethane acrylate compound, an epoxy acrylate compound, and a caprolactone-modified acrylate compound Resin composition which has photocurability and thermosetting containing 1 or more types of compounds.
The method of claim 1,
The photopolymerizable monomer is a resin composition having a photocurable and thermosetting comprising 5% to 30% by weight based on the total weight of the resin composition.
The method of claim 1,
The photoinitiator is a group consisting of benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides and oxime esters. Resin composition having a photocurable and thermosetting comprising at least one selected from.
The method of claim 1,
The photoinitiator is a resin composition having a photocurable and thermosetting comprising 0.5 to 20% by weight based on the total weight of the resin composition.
The method of claim 1,
The thermosetting functional group is a resin composition having a photocurable and thermoset of at least one selected from the group consisting of an epoxy group, oxetanyl group, a cyclic ether group and a cyclic thio ether group.
The method of claim 1,
The thermosetting binder is a resin composition having a photocurable and thermosetting contained in an amount corresponding to 0.5 to 2.0 equivalents to 1 equivalent of the carboxyl group of the acid-modified oligomer.
The method of claim 1,
solvent; And at least one selected from the group consisting of an epoxy curing agent, a thermosetting binder catalyst, a pigment, and an additive.
delete delete delete delete delete delete delete

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